supplementary materials
Diaquabis(5-carboxy-2-methyl-1H-imidazole-4-carboxylato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N3,O4)cobalt(II)
The Co atom in the title compound, [Co(C6H5N2O4)2(H2O)2], is located on an inversion centre and exhibits a distorted octahedral geometry. It is trans coordinated by two N,O-bidentate 5-carboxy-2-methyl-1H-imidazole-4-carboxylate monoanionic ligands with two water molecules in the axial positions. Each ligand is stabilized by a strong, almost symmetrical, hydrogen bond. Intermolecular N-H
O hydrogen bonds link the molecules into layers, which are further linked into a three-dimensional supramolecular framework through O-HO hydrogen-bonding interactions involving the water molecules.
Preparation of [Co(H2MIA)2(H2O)2]: A heavy-walled prex tube containing a
mixture of Co(OAc)2.6H2O (0.0285 g, 0.1 mmol), 2-methyl
-1H-imidazole-4,5-dicarboxylic acid (0.034 g, 0.2 mmol), 0.65 mol/L NaOH solutions (0.3 ml) and H2O (2 ml) was frozen in liquid
N2, sealed under vacuum and placed inside an oven at 150 °C. The red single
crystals (I) suitable for X-ray analysis were then obtained after heating of 3 d. Yield: 0.026 g, 60%. Analysis, calculated for C12H14CoN4O10 (433.20): C
33.27, H 3.26, N 12.93%; found: C 33.12, H 3.36, N 12.90%.
All H atoms attached to C atoms and N atom were fixed geometrically and treated
as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N—H =
0.86 Å with Uiso(H) = xUeq(C or N) where x=1.2 for
C(aromatic) or N and 1.5 for methyl group.. H atoms of water molecule were
located in difference Fourier maps and included in the subsequent refinement
using restraints (O—H= 0.85 (1)Å and H···H= 1.39 (2) Å) with
Uiso(H) = 1.5Ueq(O).In the final stage of refinement they
coordinates were fixed.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
Diaqua(5-carboxy-2-methyl-1
H-imidazole-4-carboxylato-\
κ2N3,
O4)cobalt(II)
top
Crystal data top
| [Co(C6H5N2O4)2(H2O)2] | F(000) = 884 |
| Mr = 433.20 | Dx = 1.805 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 3494 reflections |
| a = 6.8261 (8) Å | θ = 2.9–28.1° |
| b = 13.9705 (16) Å | µ = 1.14 mm−1 |
| c = 16.7173 (19) Å | T = 291 K |
| V = 1594.2 (3) Å3 | Block, red |
| Z = 4 | 0.38 × 0.18 × 0.16 mm |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 1825 independent reflections |
| Radiation source: fine-focus sealed tube | 1459 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| φ and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.673, Tmax = 0.839 | k = −17→18 |
| 10909 measured reflections | l = −20→21 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4264P]
where P = (Fo2 + 2Fc2)/3 |
| 1825 reflections | (Δ/σ)max < 0.001 |
| 128 parameters | Δρmax = 0.33 e Å−3 |
| 3 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
| [Co(C6H5N2O4)2(H2O)2] | V = 1594.2 (3) Å3 |
| Mr = 433.20 | Z = 4 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 6.8261 (8) Å | µ = 1.14 mm−1 |
| b = 13.9705 (16) Å | T = 291 K |
| c = 16.7173 (19) Å | 0.38 × 0.18 × 0.16 mm |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 1825 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1459 reflections with I > 2σ(I) |
| Tmin = 0.673, Tmax = 0.839 | Rint = 0.025 |
| 10909 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.084 | Δρmax = 0.33 e Å−3 |
| S = 1.08 | Δρmin = −0.33 e Å−3 |
| 1825 reflections | Absolute structure: ? |
| 128 parameters | Flack parameter: ? |
| 3 restraints | Rogers parameter: ? |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Co1 | 0.5000 | 0.5000 | 0.5000 | 0.02327 (13) | |
| O1 | 0.4610 (2) | 0.37350 (9) | 0.87496 (7) | 0.0384 (3) | |
| O2 | 0.5322 (2) | 0.52489 (10) | 0.84444 (8) | 0.0353 (3) | |
| O3 | 0.5701 (2) | 0.62758 (8) | 0.72576 (7) | 0.0354 (3) | |
| H3 | 0.545 (3) | 0.5850 (17) | 0.7866 (15) | 0.053* | |
| O4 | 0.5556 (2) | 0.60690 (8) | 0.59313 (7) | 0.0321 (3) | |
| O5 | 0.7904 (2) | 0.46448 (11) | 0.49466 (6) | 0.0356 (3) | |
| H1W | 0.8536 | 0.4646 | 0.4530 | 0.053* | |
| H2W | 0.8482 | 0.4340 | 0.5309 | 0.053* | |
| N1 | 0.47986 (19) | 0.41778 (10) | 0.60525 (8) | 0.0234 (3) | |
| N2 | 0.4548 (2) | 0.32451 (10) | 0.71031 (8) | 0.0273 (3) | |
| H2 | 0.4385 | 0.2738 | 0.7387 | 0.033* | |
| C1 | 0.4181 (4) | 0.24506 (13) | 0.57651 (11) | 0.0446 (5) | |
| H1A | 0.4148 | 0.2657 | 0.5218 | 0.067* | |
| H1B | 0.2958 | 0.2152 | 0.5900 | 0.067* | |
| H1C | 0.5228 | 0.2000 | 0.5837 | 0.067* | |
| C2 | 0.4504 (3) | 0.32885 (12) | 0.62924 (10) | 0.0269 (4) | |
| C3 | 0.4899 (2) | 0.41492 (12) | 0.73939 (10) | 0.0232 (3) | |
| C4 | 0.5065 (2) | 0.47207 (13) | 0.67325 (10) | 0.0228 (3) | |
| C5 | 0.4943 (2) | 0.43642 (13) | 0.82581 (10) | 0.0268 (4) | |
| C6 | 0.5460 (2) | 0.57575 (12) | 0.66241 (10) | 0.0248 (3) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Co1 | 0.0353 (2) | 0.0211 (2) | 0.0134 (2) | −0.00068 (12) | −0.00038 (11) | 0.00064 (11) |
| O1 | 0.0641 (9) | 0.0341 (7) | 0.0171 (6) | 0.0043 (6) | 0.0036 (6) | 0.0033 (5) |
| O2 | 0.0582 (9) | 0.0314 (7) | 0.0163 (6) | 0.0004 (6) | −0.0036 (5) | −0.0031 (5) |
| O3 | 0.0631 (9) | 0.0227 (6) | 0.0205 (6) | −0.0040 (6) | −0.0022 (6) | −0.0050 (5) |
| O4 | 0.0538 (8) | 0.0232 (6) | 0.0194 (6) | −0.0038 (6) | −0.0007 (5) | 0.0001 (5) |
| O5 | 0.0367 (7) | 0.0506 (8) | 0.0195 (6) | 0.0070 (7) | 0.0023 (5) | 0.0063 (5) |
| N1 | 0.0350 (7) | 0.0204 (7) | 0.0148 (7) | −0.0014 (5) | −0.0013 (5) | −0.0008 (5) |
| N2 | 0.0412 (8) | 0.0223 (7) | 0.0186 (7) | −0.0018 (6) | 0.0003 (6) | 0.0027 (5) |
| C1 | 0.0819 (15) | 0.0254 (9) | 0.0265 (10) | −0.0102 (10) | −0.0024 (10) | −0.0040 (7) |
| C2 | 0.0389 (9) | 0.0228 (8) | 0.0189 (8) | −0.0005 (7) | −0.0004 (7) | −0.0001 (6) |
| C3 | 0.0296 (8) | 0.0220 (8) | 0.0180 (8) | 0.0015 (6) | −0.0002 (6) | −0.0005 (6) |
| C4 | 0.0304 (8) | 0.0215 (8) | 0.0166 (8) | 0.0004 (6) | −0.0004 (6) | −0.0015 (6) |
| C5 | 0.0328 (9) | 0.0292 (10) | 0.0185 (9) | 0.0053 (6) | −0.0004 (6) | −0.0004 (7) |
| C6 | 0.0344 (8) | 0.0216 (8) | 0.0186 (8) | 0.0010 (6) | −0.0007 (6) | −0.0019 (6) |
Geometric parameters (Å, °) top
| Co1—O5 | 2.0453 (14) | O5—H2W | 0.8386 |
| Co1—O5i | 2.0453 (14) | N1—C2 | 1.321 (2) |
| Co1—N1i | 2.1057 (14) | N1—C4 | 1.379 (2) |
| Co1—N1 | 2.1057 (14) | N2—C2 | 1.357 (2) |
| Co1—O4i | 2.1904 (12) | N2—C3 | 1.374 (2) |
| Co1—O4 | 2.1904 (12) | N2—H2 | 0.8600 |
| O1—C5 | 1.225 (2) | C1—C2 | 1.482 (2) |
| O2—C5 | 1.301 (2) | C1—H1A | 0.9600 |
| O2—H3 | 1.28 (2) | C1—H1B | 0.9600 |
| O3—C6 | 1.2933 (19) | C1—H1C | 0.9600 |
| O3—H3 | 1.19 (2) | C3—C4 | 1.368 (2) |
| O4—C6 | 1.239 (2) | C3—C5 | 1.476 (2) |
| O5—H1W | 0.8190 | C4—C6 | 1.485 (2) |
| | | |
| O5—Co1—O5i | 180.0 | C2—N2—C3 | 108.42 (14) |
| O5—Co1—N1i | 91.87 (5) | C2—N2—H2 | 125.8 |
| O5i—Co1—N1i | 88.13 (5) | C3—N2—H2 | 125.8 |
| O5—Co1—N1 | 88.13 (5) | C2—C1—H1A | 109.5 |
| O5i—Co1—N1 | 91.87 (5) | C2—C1—H1B | 109.5 |
| N1i—Co1—N1 | 180.0 | H1A—C1—H1B | 109.5 |
| O5—Co1—O4i | 88.36 (5) | C2—C1—H1C | 109.5 |
| O5i—Co1—O4i | 91.64 (5) | H1A—C1—H1C | 109.5 |
| N1i—Co1—O4i | 77.84 (5) | H1B—C1—H1C | 109.5 |
| N1—Co1—O4i | 102.16 (5) | N1—C2—N2 | 110.00 (15) |
| O5—Co1—O4 | 91.64 (5) | N1—C2—C1 | 125.79 (15) |
| O5i—Co1—O4 | 88.36 (5) | N2—C2—C1 | 124.21 (16) |
| N1i—Co1—O4 | 102.16 (5) | C4—C3—N2 | 105.35 (14) |
| N1—Co1—O4 | 77.84 (5) | C4—C3—C5 | 132.11 (17) |
| O4i—Co1—O4 | 180.000 (1) | N2—C3—C5 | 122.46 (16) |
| C5—O2—H3 | 117.1 (11) | C3—C4—N1 | 109.54 (15) |
| C6—O3—H3 | 113.7 (11) | C3—C4—C6 | 133.06 (15) |
| C6—O4—Co1 | 114.58 (10) | N1—C4—C6 | 117.40 (14) |
| Co1—O5—H1W | 123.2 | O1—C5—O2 | 123.94 (16) |
| Co1—O5—H2W | 123.2 | O1—C5—C3 | 120.47 (16) |
| H1W—O5—H2W | 111.5 | O2—C5—C3 | 115.58 (15) |
| C2—N1—C4 | 106.68 (14) | O4—C6—O3 | 124.21 (15) |
| C2—N1—Co1 | 140.96 (12) | O4—C6—C4 | 117.79 (14) |
| C4—N1—Co1 | 112.35 (11) | O3—C6—C4 | 118.00 (14) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O2 | 1.19 (2) | 1.28 (2) | 2.4619 (18) | 168 (2) |
| O5—H1W···O2ii | 0.82 | 1.98 | 2.7920 (18) | 171 |
| O5—H2W···O1iii | 0.84 | 1.95 | 2.7789 (17) | 172 |
| N2—H2···O3iv | 0.86 | 2.13 | 2.9564 (18) | 162 |
| Symmetry codes: (ii) −x+3/2, −y+1, z−1/2; (iii) x+1/2, y, −z+3/2; (iv) −x+1, y−1/2, −z+3/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O2 | 1.19 (2) | 1.28 (2) | 2.4619 (18) | 168 (2) |
| O5—H1W···O2i | 0.82 | 1.98 | 2.7920 (18) | 171 |
| O5—H2W···O1ii | 0.84 | 1.95 | 2.7789 (17) | 172 |
| N2—H2···O3iii | 0.86 | 2.13 | 2.9564 (18) | 162 |
| Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1/2, y, −z+3/2; (iii) −x+1, y−1/2, −z+3/2. |
This work was supported by the National Natural Science Foundation of China
(grant No. 20662007).
Bruker (1998). SHELXTL (Version 5.10), SAINT (Version 5.10) and SMART (Version 5.0). Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.
Liu, Y., Kravtsov, V., Larsen, R. & Eddaoudi, M. (2006). Chem. Commun. pp. 1488–1490.
Liu, Y., Kravtsov, V., Walsh, R. D., Poddar, P., Srikanth, H. & Eddaoudi, M. (2004). Chem. Commun. pp. 2806–2807.
Nie, X.-L., Wen, H.-L., Wu, Z.-S., Liu, D.-B. & Liu, C.-B. (2007). Acta Cryst. E63, m753–m755.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
![[Figure 1]](./dn2222fig1thm.gif)
![[Figure 2]](./dn2222fig2thm.gif)
Recently, our group (Nie et al., 2007) described the structure of diaquabis [2-methyl-1H-imidazole-4,5-dicarboxylato(1-)]cadmium (II) as a three-dimensional network of [Cd(H2MIA)2(H2O)2] molecules held together by hydrogen-bonding interactions. The present centrosymmetric Co complex is similiar to the Cd complex, but there are some differences in their structures.
The molecule of (I) is a discrete neutral monomer, in which the asymmetric unit contains one-half of the [Co(H2MIA)2(H2O)2] formula unit. The Co atom lies on a crystallographic inversion center and has a slightly distorted octahedral geometry. Two coordinated water molecules occupy the apical positions. The equatorial plane contains two bidentate 2-methyl-1H-imidazole-4,5-dicarboxylic acid monoanionic ligands which display a strong intramolecular O—H···O symmetrical hydrogen bond with a short O···O distance of 2.462 (2) Å (Fig. 1; Table 1). Similar strong intramolecular hydrogen bondings has been already reported with this ligand (Liu et al., 2004; Liu et al., 2006).
Owing to the location of the Co on an inversion center, the two chelate rings are coplanar, with a mean deviation 0.042 (2) Å, whereas in the Cd complex, the two chelate rings are shifted with a distance between the two planes of 0.5615 Å.. In the Cd complex, N—H···O hydrogen bonds link the molecules into chains which are further linked to a three-dimensional supramolecular framework via O—H···O hydrogen bonds whereas in the title complex, N—H···O hydrogen bonds (Table 1) link the molecules into a two-dimensional layers (Fig. 2). These layers are further linked through O—H···O (Table 1) involving the coordinated water O atoms and two carboxy O atoms to form a three-dimensional supramolecular framework. The Cd complex crystallizes in Monoclinic, space group P 21/c whereas the Co complex belongs to the orthorhombic, Pbca space group.